Polyurethane foam(PU foam) primarily consist of polyurethane as their main component. The raw materials primarily include polyisocyanates and polyols, with the addition of various additives, the most crucial of which are a series of foaming agents related to the foaming process. These additives lead to the production of a significant amount of foam within the reaction product, resulting in polyurethane foam products. This article provides a brief overview of the raw materials used in producing PU foam and the foaming agents.

1.Polyisocyanates

The most commonly used polyisocyanates in the industrial production of polyurethane foams include toluene diisocyanate (TDI), polymethylene polyphenyl isocyanate (PAPI), diphenylmethane diisocyanate (MDI), and liquid MDI (L-MDI).



TDI

TDI is mainly used in the production of polyurethane flexible foams. MDI has higher reactivity than TDI, lower volatility, and some modified forms of MDI can be used as substitutes for TDI in the production of polyurethane flexible foams, including high-density polyurethane foam and the manufacturing of semi-rigid or microcellular polyurethane elastomers.

PAPI, also known as crude MDI or polymerized MDI, typically has an average molecular weight ranging from 30 to 400, with an NCO content of 31% to 32%. In the field of foam plastics, PAPI and modified PAPI are primarily used to produce various polyurethane rigid foams, with some also used in the production of high-rebound flexible foams, integral skin foams, and semi-rigid foams. PAPI can be mixed with TDI to manufacture cold-cure, high-rebound foam plastics.

2.Polyether and Polyester Polyols

2.1Polyether Polyols

Polyether polyols used for producing polyurethane flexible foams are generally long-chain, low-functionality polyethers. In the formulation of flexible foams, the functionality of polyether polyols is usually between 2 and 3, with an average molecular weight ranging from 2000 to 6500. Polyether triols are most commonly used in flexible foams, typically initiated with glycerol (propane-1,2,3-triol) and obtained through ring-opening polymerization with 1,2-epoxy propane or copolymerization with a small amount of ethylene oxide, with a molecular weight generally falling within the range of 3000 to 7000.



Polyether Polyols

High-activity polyether polyols are mainly used for high-rebound flexible foams and can be used in the production of semi-rigid foams and other foam products. Some polyether diols can be used as auxiliary materials, mixed with polyether triols in flexible foam formulations. Low unsaturation and high molecular weight polyether polyols are used for the production of soft foams, reducing the amount of TDI required.

Polyether polyols used in rigid foam formulations are generally high-functionality, high hydroxyl value polyether polyols to achieve sufficient cross-linking and rigidity. The hydroxyl value of polyether polyols for rigid foam formulations is typically in the range of 350 to 650 mg KOH/g, with an average functionality of 3 or higher. Rigid foam formulations often use a combination of two types of polyether polyols, with an average hydroxyl value of around 4000 mg KOH/g.

Semi-rigid foam formulations often use some high molecular weight polyethers, especially high-activity polyether triols, and some high-functionality, low molecular weight polyether polyols from rigid foam formulations.

2.2Polyester Polyols

Low-viscosity aliphatic polyester polyols, such as hexanediol adipate diols with a hydroxyl value of approximately 56 mg KOH/g, or slightly branched polyester polyols, can be used for producing polyester-based polyurethane flexible foams. Polyester polyols have high reactivity. Currently, block polyurethane foam made from polyester is only used in a few fields such as auxiliary materials for clothing.



Polyester Polyols

Aromatic polyester polyols, synthesized from dicarboxylic acids (such as phthalic anhydride, terephthalic acid, etc.) and small-molecule diols (such as ethylene glycol, etc.) or polyols, are used to produce polyurethane rigid foams and polyisocyanurate rigid foams. Lower hydroxyl value polyester polyols derived from phthalic anhydride can also be used for high-rebound flexible foams, integral skin foams, semi-rigid foams, and non-foam polyurethane materials.

2.3Polymer Polyols

Polymer polyols, including rigid styrene, acrylonitrile homopolymers, copolymers, and grafted polymers, act as organic "fillers" to enhance load-bearing performance. Polymer polyols are used in the production of high-hardness flexible block foams, high-rebound foams, thermoplastic flexible foams, semi-rigid foams, self-skinning foams, and reaction injection molded (RIM) products. They can reduce product thickness, lower foam density to reduce costs, increase foam plastic cell opening, and impart flame retardant properties to the products.



Polymer Polyols

Polyurea polyols (PHD dispersions) are a special class of polymer-modified polyols used in high-rebound flexible foams, semi-rigid foams, and soft foams, but their presence in the market is limited.

There are also some special polyols used for the production of polyurethane foams, such as vegetable oil-based polyols, rosin-based polyester polyols, and polymer polyesters. These are not described in detail in this article.

Many factors affect the foaming process and final product quality when manufacturing polyurethane flexible foam. Among these, natural environmental factors such as temperature, air humidity, and atmospheric pressure play crucial roles. These factors significantly influence foam density, hardness, elongation rate, and mechanical strength.

1. Temperature:

Polyurethane foaming reaction is highly sensitive, with temperature being a key control factor. As material temperature rises, the foaming reaction accelerates. In sensitive formulations, excessively high temperatures can pose risks like core burning and ignition. Generally, it's essential to maintain consistent temperatures for polyol and isocyanate components. Increasing temperature leads to a corresponding decrease in foam density during foaming.

Particularly in summer, elevated temperatures increase reaction speed, resulting in decreased foam density and hardness, increased elongation rate, yet enhanced mechanical strength. To counter hardness reduction, adjusting the TDI index is advisable. Manufacturers must adjust process parameters according to seasonal and regional temperature variations to ensure product quality stability.

2. Air Humidity:

Air humidity also affects the foaming process of polyurethane flexible foam. Higher humidity causes reactions between isocyanate groups in the foam and airborne moisture, leading to reduced product hardness. Increasing TDI dosage during foaming can compensate for this effect. However, excessive humidity can raise curing temperatures, potentially causing core burning. Manufacturers need to carefully adjust foam process formulations and parameters in humid environments to ensure product quality and stability.

3. Atmospheric Pressure:

Atmospheric pressure is another influencing factor, especially in areas at different altitudes. Using the same formulation at higher altitudes results in relatively lower foam product density. This is due to atmospheric pressure variations affecting gas diffusion and expansion during foaming. Manufacturers operating in high-altitude regions should take note of this and may need to adjust formulations or process parameters to meet quality requirements.



In conclusion, natural environmental factors significantly impact the foaming process and final product quality of polyurethane flexible foam. Manufacturers must adjust process parameters based on seasonal, regional, and environmental conditions to ensure stable foam density, hardness, and mechanical strength, meeting customer demands and standards.

Beginners are concerned that if the settling plate is not adjusted properly, the liquid flowing out of the nozzle may cause front surging or back surging, affecting the foaming process. Within two minutes after starting the machine, the reaction speed gradually increases, sometimes requiring adjustments to the settling plate. Adjustments to the settling plate are more critical in low-density and high-moisture-content (MC) formulas.



TDI (Toluene Diisocyanate) flow rate can be calculated to correspond to the scale value, but it is recommended to actually measure the TDI flow rate during the first foaming. Flow rate is too important; if the flow rate is not accurate, everything else will be a mess. It's best to rely on the simplest and most intuitive method of measuring the flow rate.



When mixing powders, the mixed stone powder should be left overnight and production should start the next day. For ingredients containing melamine and stone powder, it is recommended to first mix melamine with polyether for a period of time before adding the stone powder.



Foam machine formulas with long mixing chamber in the machine head or more teeth on the stirring shaft usually have less amine and lower material temperature. Conversely, foam machine formulas with short mixing chamber in the machine head or fewer teeth on the stirring shaft usually have more amine and higher material temperature.



For the same formula, when switching between dual-spray swivel heads and single-spray swivel heads with similar nozzle cross-sectional areas, the requirements for mesh thickness and layers are similar.



For the calibration of minor material flow, one method is to measure the return flow of the minor material, and the other is to calibrate it by dividing the total amount used by the foaming time. When there is a significant difference between the two calibration methods, rely on the data from the second calibration method.



Formulas for high-quality soft foam are usually within an unstable range, such as a low TDI index, low water-to-MC ratio, low T-9 dosage, and low silicone oil dosage.

In annual fire incidents, a significant proportion of ignitions are caused by foam, including sofa fires and various ignitions from soft packaging. These incidents occur far too frequently. How can we fundamentally eliminate or reduce such events?



One effective approach is to start from the source materials, much like treating the root cause of an illness. Adding flame retardants to polyurethane foam can effectively prevent ignition.



Now, let's understand flame-retardant foam:



Flame-retardant foam, also known as fire-resistant foam, has a chemical name of polyurethane foam material, which is divided into soft foam (mainly used for furniture) and rigid foam (mainly used for insulation). Generally, it is a fireproof material synthesized by adding various flame retardants to polyurethane.



The product's fire-retardant effect meets the requirements of ASTM Standard 117 and national standards. The usage method is the same as regular foam.



The combustion of polymers is a very complex and intense oxidation reaction. The process occurs as the polymer is continuously heated by an external heat source, initiating a free radical chain reaction with oxygen in the air. This releases some heat, further intensifying the degradation of the polymer, generating more flammable gases, and making the combustion more severe.



There are two methods for the flame retardancy of fire-resistant foam:



One is to chemically introduce flame-retardant elements or groups containing flame-retardant new elements into the molecular structure of the foam. The other method is to add compounds containing flame-retardant elements to the foam. The former method uses flame-retardant substances called reactive flame retardants, while the latter method uses substances called additive flame retardants.



Currently, the vast majority of flame retardants used in foam are additive flame retardants, while reactive flame retardants are mainly used in thermosetting resins such as epoxy resins and polyurethanes. The primary function of flame retardants is to interfere with the three basic elements required for combustion: oxygen, heat, and fuel. This can generally be achieved through the following means:



Flame retardants can produce heavier non-flammable gases or boiling liquids that cover the surface of the foam, interrupting the connection between oxidation and fuel.



By absorbing heat through decomposition or sublimation, flame retardants reduce the surface temperature of the polymer.



Flame retardants generate a large amount of non-flammable gases, diluting the concentration of flammable gases and oxygen in the combustion area.



Flame retardants capture radical free radicals, interrupting the chain reaction of oxidation.

The internal temperature of foam is as indispensable as vitality is to a person. If the post-cure temperature of the sponge is too low, its physical properties will not be optimal, and there will be significant fluctuations in these properties.



Once the foam is well developed, its internal temperature rapidly rises to over 120 degrees Celsius due to the exothermic reaction occurring under poor heat dissipation conditions, becoming one of the fire hazard risks.



The internal temperature of the foam is crucial for forming its superior properties. Foam matured at specific external temperatures exhibits exceptionally superior physical properties like tensile strength. Some calculate the foam temperature through formulas, while others use software to input formulas and automatically calculate the internal temperature of the foam. So, what factors influence the internal temperature of the foam? Is it significant to know these factors? It's akin to how modern phone cameras are high-resolution, but does that render professional photography useless? Are adjustments like aperture, focal length, and exposure time pointless? To better control things, one must grasp more of the key variables of that thing. Let's start with basic principles to understand the changes in internal foam temperature.



First, let's grasp a few basic rules.



The temperature of a space is directly proportional to the amount of heat energy injected into that space and inversely proportional to its size.

For example, if 10 kilojoules of heat are distributed in an 8-liter space, the temperature of that space is 20 degrees Celsius. If the same 10 kilojoules of heat are distributed in a 4-liter space, the temperature becomes 40 degrees Celsius.

The amount of heat input is directly proportional to the heat input value and the speed of heat input.

For instance, if 100 kilojoules of heat are released at speed "v," the heat input is "A." If the same 100 kilojoules of heat are released at 2v speed, the heat input becomes 2A.

The size of a space is directly proportional to the absolute temperature.

For example, a 1-liter space at 0 degrees Celsius becomes 1.366 liters at 100 degrees Celsius because (273.15 + 100)/(273.15 + 0) = 1.366.

The size of a space is inversely proportional to atmospheric pressure.

The lag in methane vaporization needs to be considered.

Next, let's examine how fine-tuning the formula affects the internal foam temperature.



Since this is fine-tuning, we'll approximate that the surrounding environment remains unchanged before and after the adjustments. Let's consider the effects of adjusting water and methane on the internal foam temperature.

For example, if a formula increases methane by 5%, we can be certain that the internal foam temperature decreases because methane vaporization absorbs heat, reducing the heat input to the foam, and increasing the space to accommodate heat. Similarly, if the water content is increased by 5%, the added water releases heat upon injection into the foam, raising the heat input, and the reaction of the added water generates gas, increasing the space for heat. So, does the internal foam temperature increase or decrease in this case? Experience indicates that the internal foam temperature increases. This suggests that the increased heat input due to this change contributes more to the increase in internal foam temperature than the gas produced by water diluting the temperature.



The changes involving foam index, heat release, and heat dissipation all increasing can make it difficult to intuitively guess whether the internal foam temperature will rise or fall. One might need to insert a probe after foaming to compare internal temperatures or calculate to reach a conclusion.



For calculations, several formulas (algebraic expressions) derived from the earlier basic rules are needed, along with some data: the heat released when water reacts with TDI to form carbon dioxide in kilojoules per mole, the heat absorbed during methane vaporization in kilojoules per mole. To estimate the total foam internal temperature, one must know the heat released when forming amino methyl formate, urea methyl formate, urea, and biuret (polyurea), in kilojoules per mole, and the reaction rate (reaction time).



This also explains why the density calculated from the foam index drastically differs from the theoretical and actual values for foams without fillers at 50 densities. The lower the density, the more closely the theoretical and actual values of foam density match.